Method of making an ion-exchange material from light oil acid sluidges



Oct. 18, 1949. BIRCHER, ]R 2,485,352

METHOD OF MAKING AN ION-EXCHANGE MATERIAL FROM LIGHT OIL ACID SLUDGES 7 Filed Sept. 7, 1946 Carbonization Sulturic Acid or Oleum Light Coke Oil Sulfuric Acid Acid Light Oil Purified Stearn Concentrated Hard Sludge Light Oils. Sulfuric Acid with Low Acid Volatilized Content Y Crushed Sulfuric Acid Washer Patented O t. 18, 1949 UNlTED STATES METHOD OF MAKING AN ION-EXCHANGE MATERIAL FROM LIGHT .OIL ACID SLUDGES PATEN orFiCB John R. Bircher, In, Colombo.. Ohio," ands-nor,

assignm by mesne to Inter-lake Chemical- Corporation of DelawarepOleveland, Ohio, a

I corporation of Delaware Application September 7, 1946, Serial .2 Claims. (ct-253479),

period of time principally in the water-softeningindustry. A number of new uses for these ionexchange materials have arisen in the past few years which require greater amounts of the ionexchange materials at lower costs. The present problem in the production of ion-exchange materials from a commercial standpoint, is the lowcost production of ion-exchange materials from cheap source ingredients while maintaining high efllciency as an exchanger. The so-called carbonaceous zeolites, which. are manufactured by treating carbonaceous matter with concentrated sulfuric acid, have been proposed as one answer to this problem, but these carbonaceous zeolites are not completely satisfactory either. from the point of ion-exchange properties or cost.

It is an object of this invention, therefore, to provide an ion-exchange material that is inexpensive and which is highly eflicient as an ionexchange material.

Another object of this invention is to provide a method of converting a waste product of the coal carbonization industry into an ion-exchange material. 7

Other objects and advantages of this invention will become apparent from the following detailed description thereof when read in conjunction with the accompanying drawing, in which the single figure represents a flow sheet of the production of the ion-exchange material comprising the present invention.

It has been found that very satisfactory ionexchange materials may be. produced from the sludge resulting from the acidification of light oils derived from the carbonization of coal. Coal is carbonized to produce coke and various byproducts, among which is a light oil consisting essentially of homologous members of the henzene series of hydrocarbons and alkylated derivatives, together with a very small amount of dissolved alkanes, alkenes, and alkines. This light oil is originally present in the vapor form and is recovered from the gas stream by m of an absorption oil, from. which it is' ter stripped by means of live steam. In order to 're-. move certain impurities from the light ofl, it is the present practice to treat it with oleum 20% SO:+80% of 100% H2304) or concentrated sulfuric acid or both. Following this treatment three-layers form upon. standing, the bottom consisting essentially of sulfuric acid, the middle layer being an acid sludge formed by the reaction in. sensor 2 I h of the acid with the impurities in the li ht oil. especially the unsaturated compounds therein, and the top layer'being the purified light oil. Here- 1 tofore, 'thesulfuric' acid was drained off, followed shortly by the acid sludgelayer which, due-to itshigh acid content, had to be specially treated and carted oil at considerable expense to the manu-.

' facturer.

A It isthis acid sludge, which formerly was an unwanted waste product, that forms the raw material for the ion-exchange material of the present. invention. There is a considerable variation in physical properties of this acid sludge derived from the acid'treatment of light oil, due to the variation in composition of the coal carbonized and the particular treatment given the acid sludge or light oil in each different plant. In

' oil is introduced in its highly viscous state into a cooker? which is a lead-lined vessel heated preferably by steam coils and in which are disposed anumber of spargers through which steam is forced under pressure. The'live steam which is forced through the sparg'ers and up through the acid sludge in the cooker removes the light oils or any other volatile unreacted material from the sludge so as to aid in the concentration of the sulfuric acid which, because of its greater specific gravity, collects at the-bottom of the cooker and is drained oil. The-temperature in the'cooker is preferably maintained at some point between 212 .F. and 300 F., although slight variations above or below these temperatures are not mate rial. The higher temperatures within this range. are generally more satisfactory from a commercial standpoint, since they decrease the dilution of the acid. The length of cooking necessary to satisfactorily treat any particular batch of acid sludge varies considerably, that is, from about 12 to about 56 hours-although one criterion which is indicative of the point at which the cooking is complete, is that stage at which the'sludge will just barely flow from the cooker. I v

Upon cooling, the'sludge-from the cooker'whi'ch has been largely freed of its acid content becomes quite hard and brittle and may be easily crushed prior to washing with water. The crushed sludge is washedwith water in a'vessel provided with a means of positive agitation. The water is'removed from the slurry by'filtration, using suction filters, centrifugal filters, or other type of filteraesassa sludgeisireediromtheremainingacidcom tamed therein is not material aiter that point has been reached where only 0.8-0.055 oi acid remainstherein.

At this point in the process, the sludge material has become a hydrogen-ion type iron-exchange agent, and, ii it is to be used in this iorm, is then dried. crushed and screened to size. Usually, however, some other active form, such as the sodium term, is desired in water-soitening processes. The hydrogen-ion type sludge may be converted to the sodium iorm by treatment with sodium salts in the usual manner. A number oi sodium salts may be employed in this process, for example, sodium chloride, sodium carbonate, sodium bicarbonate. etc.

In order to better enable those skilled in the art to practice the present invention, the iollowing examples representing various embodiments thereof are set iorth:

Example 1 A 500-gram sample oi an acid sludge obtained in the treatment oi crude coke oven light oil (boiling u to 185 0.) with 20% oleum (20% SOs+80% oi 100% H1504) was heated in a leadlined cooker by means oi coil steam and open steam for a period oi 30 hours at temperatures varying between 212 1''. and 312 1". At the end oi the heating period, the steam was shut 01! and the dilutejacid was withdrawn irom the cooker. The treated sludge was then poured irom the cooker and allowed to cool, at which time it was broken up andwashed with water in three separate washes, each wash containing water equal to about twice the volume oi the steamed sludge being treated. The washed sludge was then neutralized and converted into the sodium iorm oi ion exchanger by treatment with a sodium carbonate solution oi about concentration and equal in quantity at least to the' volume oi the material being treated. The excess alkali was removed by further water washing, and the fluished ion-exchange material was dried and screened. From about 250 to about 300 grams of finished ion-exchange material were obtained from the 0 al 500 grams oi acid sludge treated.

Example 2 A procedure identical with that employed in Example l.was followed in this example with the exception that 66 Be. suliuric acid was used in place oi the 20% oleum employed in Example 1. The acid sludge treated was approximatel the same composition as thattreated iniltxample 1, and between 200- and 250 grams oi the finished ion-exchange material were obtained by this manner oi treatment.

trample 3 A BOO-gram sample oi acid sludge was obtained in treatment oi the crude benzol-toluol-xylol traction oi the light oil resulting irom the carbonization oi coal which boils at a range irom 50 C. to 150' C..with a mixture oi 68 Be. suliuric acid and 20% oleum injequal portions in a manner similar to that employed in Examples 1 and 2. Further treatment oi this sample also iollowed the procedure set iorth in Examples 1 and 2 and the iinai product amounted to between 35 to about 45%, by weight, oi the original acid sludge treated.

The working capacities oi ion exchangers derived irom the coke oven light oil acid sludges usually are about 7500 to9000 grams per cubic ioot oi exchanger, although much higher capacities may be obtained with some of the acidsludges. A-ieature characteristic oi these ion-exchange materials is their detergent eiiect.

By practicing the method of this invention, a waste material, which operators oi coal carbonizin plants have heretofore been burdened with the expense oi disposing, is converted to a hig y useiul ion-exchange material having marked ionexchange activity. Since there exists quite large quantities of acid sludges as by-products oi the treatment or light oils derived from the carbonixation oi coal, there is suiilcient quantity oi these sludges to produce enough ion-exchange material to satisfy demands oi large industries which emchangers so prodced are greatly interior in ionexchange activity to those produced by cooking the sludge in the presence oi sulfuric acid as hereinabove set iorth. Other means oi heating the acid sludge in the cooker than by steam coils and by live steam may be employed, although the means above set forth are preferred. Examples of other heating means are electrical heaters, hot water under pressure. hot air, and the like.

The words "an active form, as used throughout the specification and the attached claims, reier to ion exchangers which have been so treated as toadsorb those ions to be removed from solu- What is claimed is:

1. A method oi producing an ion exchange material, which comprises treating with sulphuric acid the light oil derived from the carbonization oi coal to produce a sludge that is insoluble in sulphuric acid, separating the sludge irom the other components, cooking the sludge by subjecting it to direct contact with steam at temperatures between 212 I". and 800 1". to remove volatiles, and washing the cooked sludgeuntil not more than about 0.3% acid remains.

2. A method oi producing an ion exchange material, which comprises treating with sulphuric acid the light oil derived irom the carbonization oi coal to provide three layers in the reactant vessel including a lower layer oi sulphuric acid, a middle layer oi sludge and an upper layer of light oil, withdrawing the middle layer oi sludge, cooking the sludge by subjecting it to direct contact with steam at temperatures ranging irom 212 F. to 300" I". inorder to remove volatiles therefrom, and washing the sludge to remove iree-acid until not more than 0.3% iree-acid remains therein.

JOHN R. BIRCHER, .112.

REFERENCES CITED The iollowing reierences are of record in the ilie oi this patent:

UNI'I'ED sTA'rzs PATENTS Number Name Date 2,191,060 Liebknecht Feb. 20, 1940 2,337,500 flavelli Dec. 21, 1943 

